CN110732346A - polymetallic methanation catalyst, and preparation method and application thereof - Google Patents
polymetallic methanation catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses multi-metal methanation catalysts, which are based on perovskite type composite oxides and highly dispersed in SBA-15 pore channels of a mesoporous molecular sieve, wherein the perovskite type composite oxides are La1‑xAxB1‑yNiyO3X is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, A is at least of alkali metals, alkaline earth metals and rare earth metals, B is at least of transition metals, the load of La is 1-10 mol%, the load of A is 1-10 mol%, the load of B is 1-10 mol%, and the load of Ni is 1-10 mol%The design and preparation of the catalyst provide thought and theoretical guidance.
Description
Technical Field
The invention belongs to the technical field of catalysts and preparation thereof, and particularly relates to perovskite-based composite oxide multi-metal methanation catalysts highly dispersed in SBA-15 pore channels, and a preparation method and application thereof.
Background
The Ni-based catalyst has good activity, methane selectivity and relatively low price, and is a methanation catalyst with the most industrial application potential at present, basic research and industrial practice for many years show that main factors influencing the reaction activity and stability of the Ni-based methanation catalyst include (1) sintering and agglomeration of metal particles, wherein metal Ni grains are easy to be thermally agglomerated in the catalytic reaction process due to the fact that CO methanation is a strong exothermic reaction, so that the number of surface catalytic active centers is reduced, and the activity of the catalyst is reduced, (2) carbon deposition, wherein in the methanation process, a side reaction for generating carbon exists besides CO methanation reaction, and generated carbon species block catalyst channels, cover the active centers or strip the surface of a carrier, so that the activity of the catalyst is reduced, the change of the surface property and the thermal stability of the active centers Ni by introducing an assistant metal is a key method for improving the activity, the carbon deposition resistance and the sintering resistance of the Ni-based catalyst at present, , the high uniform dispersion and strong interaction of the assistant metal and the assistant metal are a key method for improving the activity, the optimal catalytic activity and the stability of the catalyst are prepared by introducing the assistant metal precipitation, and the high-precipitation method for improving the hydrothermal dispersion and precipitation of the catalyst are needed.
Perovskite Type Oxides (PTOs) have become hot points of research in the field of modern industrial catalysis due to the advantages of controllable composition and structure, low price and the like. The basic structure of PTOs is ABO3Wherein A is an alkali metal ion, an alkaline earth metal ion and a rare earth metal ion with a larger radius, and B is a transition metal ion with a smaller radius. PTOs as precursors of catalyst active metals have the following advantages: (1) because A and B are distributed in the crystal lattice according to the atomic size, the reduced metal can reach a highly ordered dispersed state; (2) because metal bonds exist between A and B in the crystal lattice, the reduced metals A and B have strong interaction, and are beneficial to inhibiting the migration and aggregation of the reduced metals A and B at high temperature; (3) because the elements at the A and B positions can be replaced by other metals, the physicochemical properties of the alloy have flexible regulation and control. When other auxiliary metals B' are partially used for replacing the metal B, the structure, surface property and reduction property of the PTOs are changed, so that the catalytic performance of the PTOs is changed; (4) the active site can be realized by regulating and controlling the reduction process of PTOsThe effective regulation of the structure, in turn, affects its catalytic performance. Because of the small specific surface area (< 10 m) of PTOs2The grain size is larger than 10nm), the long-term stability is poor and the like, which are not beneficial to the industrial application. Therefore, how to effectively improve the dispersity and long-term stability of metal particles obtained by PTOs reduction is a key problem to be solved urgently. In addition, a stable support is very critical for high temperature methanation reaction systems. The ordered mesoporous material has the advantages of good structural performance, ultrahigh specific surface area, stable framework structure and the like, and has good application value in the aspects of catalysis, environment, energy and the like. However, how to effectively utilize the high surface area and the pore structure of the ordered mesoporous material to promote the dispersion of the metal and inhibit the sintering of the metal particles in the reaction process still needs to be solved.
Therefore, needs to be found for a polymetallic methanation catalyst with highly dispersed active metal and assistant metal and strong interaction, and excellent high temperature resistance and stability are needed while high activity is ensured.
Disclosure of Invention
The invention aims to provide multi-metal methanation catalysts which are based on perovskite type composite oxides, have strong interaction between active metals and auxiliary metals and are highly dispersed in SBA-15 pore channels.
Another objects of the invention are to provide methods of making the multi-metal methanation catalyst.
Still another object of the present invention is to provide applications of the multi-metal methanation catalyst in the production of methane from syngas.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the th aspect of the invention provides multi-metal methanation catalysts, which are multi-metal methanation catalysts based on perovskite type composite oxides and highly dispersed in the pore channels of the mesoporous molecular sieve SBA-15, wherein the perovskite type composite oxides are La1-xAxB1-yNiyO3X is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, A isAt least alkali metals, alkaline earth metals and rare earth metals, B is at least transition metals, the loading amount of La is 1-10 mol%, the loading amount of A is 1-10 mol%, the loading amount of B is 1-10 mol%, and the loading amount of Ni is 1-10 mol%.
The mesoporous molecular sieve SBA-15 has the pore size of 4.6-30 nm, the pore wall thickness of 3-9 nm and the pore volume of 0.8-1 cm3A/g, preferably 0.85cm3The mesoporous molecular sieve SBA-15 is a molecular sieve material with larger pore diameter at present, and the SBA-15 has larger pore diameter size, thicker pore wall structure and better hydrothermal stability than the traditional MCM-41 while keeping a highly ordered two-dimensional hexagonal structure, so that the mesoporous molecular sieve shows -wide potential application prospects in the fields of adsorption, catalysis, biomedicine, new material processing and the like.
The alkali metal is at least of Rb and Cs.
The alkaline earth metal is at least of Mg, Ca, Sr and Ba.
The rare earth metal is at least of Ce and Sm.
The transition metal is at least of Fe, Co, Ru, Rh, Cu and Mo.
The second aspect of the invention provides preparation methods of the multi-metal methanation catalyst, which comprises the following steps:
, dissolving a lanthanum-containing compound, a metal A precursor, a metal B precursor and a nickel-containing compound in deionized water, stirring and dissolving, then adding a complexing agent and a solvent, wherein the ratio of the complexing agent to the total molar weight of the lanthanum-containing compound, the metal A precursor, the metal B precursor and the nickel-containing compound is (1-1.5): 1, and stirring to uniformly mix;
and secondly, soaking the mesoporous molecular sieve SBA-15 in the prepared mixed solution at room temperature for 2-12 hours, drying in vacuum at 40-60 ℃ for 6-8 hours after soaking, presintering at 300-500 ℃ for 2-3 hours, calcining at 600-800 ℃ for 4-6 hours, grinding into fine powder, and filtering by using a 100-mesh sample separation sieve to obtain the multi-metal methanation catalyst.
The lanthanum-containing compound isLanthanum nitrate (La (NO)3)3·nH2O)。
The metal A precursor is a compound containing kinds of metals including Rb, Cs, Mg, Ca, Sr, Ba, Ce and Sm, preferably magnesium nitrate (Mg (NO)3)2·6H2O), calcium nitrate (Ca (NO)3)2·4H2O), cerium nitrate hexahydrate (Ce (NO)3)3·6H2O)。
The precursor of metal B is a compound containing kinds of metals including Fe, Co, Ru, Rh, Cu and Mo, preferably ferric nitrate (Fe (NO)3)3·9H2O), cobalt nitrate (Co (NO)3)2·6H2O), ammonium molybdate (H)32Mo7N6O28)。
The nickel-containing compound is nickel nitrate (Ni (NO)3)2·6H2O), nickel acetate (Ni (CH)3COO)2) kinds of (1).
The complexing agent is of citric acid, sodium acetate and glycine.
The solvent is ethylene glycol.
The third aspect of the invention provides application of the multi-metal methanation catalyst in preparation of methane from synthesis gas.
The conditions for preparing methane from the synthesis gas are as follows: the volume space velocity of the synthesis gas is 3000-30000 mL/g.h, the pressure is from normal pressure to 3.0Mpa, the temperature is 250-600 ℃, and H in the synthesis gas2The ratio of/CO is 2-4.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the multi-metal methanation catalyst disclosed by the invention shows excellent catalytic activity and methane selectivity in the reaction of preparing methane from synthesis gas, has a wider operation temperature range, and has activity in a temperature range of 250-600 ℃, wherein the activity of the catalyst is the best in the temperature range of 300-450 ℃, the CO conversion rate can reach more than 100%, and the methane selectivity reaches more than 94%.
The multi-metal methanation catalyst prepared by the method has the advantages of excellent high temperature resistance stability (catalytic activity is not reduced after high-temperature calcination for 2h at 700 ℃), longer service life (catalytic activity is not reduced in a 300h service life experiment) and the like. The multi-metal methanation catalyst prepared by the invention has the advantages that the active metal and the assistant metal are highly uniformly dispersed and have strong interaction, so that the assistant catalytic effect of the assistant metal is exerted to the maximum extent.
In the preparation process of the multi-metal methanation catalyst, the citric acid is added to serve as a complexing agent, so that the formation of the perovskite type composite oxide is ensured, and the size of active component particles can be refined and uniformly dispersed in pore channels of the carrier; meanwhile, due to the limited action of the carrier pore canal, the sintering and agglomeration of metal are inhibited in the catalyst reduction and calcination processes, so that the dispersion degree of active components in the catalyst is improved, and the activity and stability of the catalyst are influenced finally.
The multi-metal methanation catalyst obtained by the invention has the advantages of high catalytic activity, good methane selectivity, excellent heat resistance, longer service life of the catalyst and the like, and has great industrial prospect. Meanwhile, the preparation method of the invention also provides thought and theoretical guidance for the design and preparation of other high-dispersion limited-range multi-metal catalysts.
Drawings
FIG. 1 is a TEM image of the vector SBA-15 used in the examples of the present invention.
FIG. 2 shows a perovskite-type composite oxide La according to the present invention1-xAxB1-yNiyO3X is more than or equal to 0 and less than 1, and y is more than or equal to 0 and less than 1.
FIG. 3 shows a perovskite-type composite oxide LaMo prepared in example 10.5Ni0.5O3HRTEM-mapping of (A).
FIG. 4 shows the LaNiO catalyst prepared in example 23TEM image of/SBA-15.
FIG. 5 is a graph comparing the catalytic performances of the catalysts of examples 2-4 and comparative examples D1-D3 when applied to methane production from synthesis gas.
Detailed Description
In order to more clearly illustrate the invention, the invention is described in further with reference to preferred embodiments it is to be understood by those skilled in the art that the following detailed description is intended to be illustrative and not restrictive, and the scope of the invention is not intended to be limited thereby.
The sources of the raw materials used in the following examples are illustrated below:
mesoporous molecular sieve SBA-15: the preparation method is self-made in a laboratory and comprises the following steps: 4.0g of triblock surfactant P123 (EO) are added under the constant temperature condition of 40 DEG C20PO70EO20M5800) (supplied by Sigma-Aldrich) was dissolved in 125g of deionized water, followed by addition of 23.6g of a 36-38% by mass HCl solution. After complete dissolution, 8.5g of tetraethoxysilane is slowly added, and vigorous stirring is maintained for 24 h. Then, 46mg of NH was added4Dissolving F in 5mL of deionized water, adding the dissolved F into the solution, transferring the mixed solution into a polytetrafluoroethylene bottle, crystallizing at 110 ℃ for 24h, filtering, washing, drying, and finally roasting the dried product at 550 ℃ for 6h (the heating rate is 1 ℃/min) to remove the template agent, thus obtaining the white powder carrier mesoporous molecular sieve SBA-15, wherein the structure is shown in figure 1, figure 1 is a TEM image of the carrier SBA-15 used in the embodiment of the invention, and the pore structure of the SBA-15 can be visually seen from figure 1, and -dimensional straight pores are tightly arranged in the (110) direction.
The raw materials used in the examples of the present invention: nickel nitrate hexahydrate, ethylene glycol, citric acid, lanthanum nitrate, ammonium molybdate, ferric nitrate nonahydrate, and cerium nitrate hexahydrate were all purchased from Shanghai Lingfeng Chemicals, Inc.
Example 1
This example is for explaining the preparation method of the perovskite-type composite oxide and the structural characteristics thereof
(1) 0.67g of lanthanum nitrate (La (NO)3)3·nH2O), 0.30g of nickel nitrate (Ni (NO)3)2·6H2O) and 0.18g of ammonium molybdate (H)32Mo7N6O28) Dissolving in 7g of deionized water, adding 1.03g of citric acid and 0.12g of ethylene glycol under stirring after complete dissolution, and stirring to uniformly mix;
(2) standing the obtained solution for 6h, anddrying at 60 deg.C for 6 hr, calcining at 350 deg.C for 2 hr, calcining at 700 deg.C for 5 hr to obtain sample, grinding into fine powder, filtering with 100 mesh sieve to obtain LaMo0.5Ni0.5O3。
The complexing process in the sample preparation process is shown in FIG. 2, and FIG. 2 shows the perovskite type composite oxide La of the present invention1-xAxB1-yNiyO3X is more than or equal to 0 and less than 1, and y is more than or equal to 0 and less than 1, and as can be seen from the figure, all metals in the prepared perovskite type composite oxide can reach atomic level dispersion. The HRTEM-mapping diagram is shown in FIG. 3, and FIG. 3 is the perovskite-type composite oxide LaMo prepared in example 10.5Ni0.5O3According to the HRTEM-mapping diagram, the distribution of metal elements La, Ni and Mo can be seen, and in a sample obtained by adopting a citric acid complexation method, the metals La, Ni and Mo are highly and uniformly dispersed and have mutual contact, so that the strong interaction and high dispersion of the promoter metal and the active metal in the catalyst can be ensured, and the promotion performance of the promoter metal is ensured to the greatest extent.
Example 2
(1) 0.30g of Ni (NO)3)2·6H2O and 0.33g La (NO)3)3·nH2Dissolving O in 7g of deionized water, adding 1.03g of citric acid and 0.12g of ethylene glycol under stirring after the O is completely dissolved, and stirring to uniformly mix;
(2) weighing 1.0g of SBA-15 (the pore size of the mesoporous molecular sieve SBA-15 is adjustable between 4.6 and 30nm, the pore wall thickness is 3 to 9nm, and the pore volume is 0.85cm3/g) white powder, adding SBA-15 white powder into the solution at room temperature for soaking for 10 hours, after the soaking is finished, drying for 8 hours in vacuum at 50 ℃, then presintering for 2 hours in air at 300 ℃, roasting for 6 hours at 600 ℃, naturally cooling to room temperature, grinding into fine powder, filtering by using a 100-mesh sample sieve to prepare the polymetallic methanation catalyst, which is marked as LaNiO3SBA-15, nickel and lanthanum loading were 5 mol%.
The prepared LaNiO3A TEM image of the/SBA-15 catalyst is shown in FIG. 4, FIG. 4 is that prepared in example 2Catalyst LaNiO3TEM image of/SBA-15. As can be seen from FIG. 4, the active components of the prepared catalyst are uniformly distributed in the pore channels of the carrier SBA-15, and the sizes of the metal particles are concentrated at 2-5 nm.
Example 3
LaMo was prepared in the same manner as in example 2 except that the amount of nickel nitrate hexahydrate was changed to 0.24g and 0.04g of ammonium molybdate was added0.3Ni0.7O3the/SBA-15 multi-metal methanation catalyst comprises 5 mol% of lanthanum, 4 mol% of nickel and a molar ratio of the nickel to the molybdenum of 7: 3.
Example 4
(1) 0.30g of nickel nitrate (Ni (NO)3)2·6H2O), 0.16g lanthanum nitrate (La (NO)3)3·nH2O) and 0.22g of cerium nitrate hexahydrate (Ce (NO)3)3·6H2O) is dissolved in 7g of deionized water, after complete dissolution, 1.03g of citric acid and 0.12g of ethylene glycol are added under stirring, and the mixture is stirred to be uniformly mixed;
(2) weighing 1.0g of SBA-15 white powder (the pore size of the mesoporous molecular sieve SBA-15 is adjustable between 4.6 and 30nm, the pore wall thickness is 3 to 9nm, and the pore volume is 0.85 cm)3/g), adding SBA-15 white powder into the solution at room temperature for soaking for 4h, after the soaking is finished, drying for 6h in vacuum at 60 ℃, then presintering for 3h in air at 500 ℃, roasting for 4h at 800 ℃, naturally cooling to room temperature, grinding into fine powder, filtering by using a 100-mesh sample sieve to obtain the polymetallic methanation catalyst, which is marked as La0.5Ce0.5NiO3SBA-15, the loading of nickel is 5 mol%, the loading of lanthanum is 2.5 mol%, and the molar ratio of lanthanum to cerium is 1: 1.
Example 5
(1) 0.09g of nickel acetate (Ni (CH)3COO)2) 0.20g of iron nitrate (Fe (NO)3)3·9H2O), 0.19g lanthanum nitrate (La (NO)3)3·nH2O), and 0.10g of magnesium nitrate (Mg (NO)3)2·6H2O) is dissolved in 7g of deionized water, and after the materials are completely dissolved, 0.37g of glycine and 0.12g of ethylene glycol are added under the stirring state, and the materials are stirred to be uniformly mixed;
(2) weighing 1.0g of SBA-15 white powder (the pore size of the mesoporous molecular sieve SBA-15 is adjustable between 4.6 and 30nm, the pore wall thickness is 3 to 9nm, and the pore volume is 0.85 cm)3/g), adding SBA-15 white powder into the solution at room temperature for soaking for 6h, after the soaking is finished, drying for 6h in vacuum at 60 ℃, then presintering for 3h in air at 350 ℃, roasting for 4h at 700 ℃, naturally cooling to room temperature, grinding into fine powder, filtering by using a 100-mesh sample sieve to obtain the polymetallic methanation catalyst, which is marked as La0.6Mg0.4Fe0.5Ni0.5O3SBA-15, nickel loading 2.5 mol%, nickel to iron molar ratio 1:1, lanthanum loading 3 mol%, lanthanum to magnesium molar ratio 6: 4.
Example 6
This example was used to compare the catalytic activity of different multimetallic methanation catalysts in the reaction of synthesis gas to methane
The multi-metal methanation catalysts prepared in the embodiments 2 to 5 are respectively filled in a fixed bed micro-reactor with the inner diameter of 8mm, and N is used before reaction2Purging air, and introducing pure H at 650 deg.C2The catalyst was reduced for 2 hours. Then, the catalytic performance of the obtained catalyst in the methanation reaction of the synthesis gas is considered. The composition of the feed gas and the catalytic reaction conditions were as follows:
the raw material gas composition is as follows: CO: 20% of H2：60％，N2：20％；
Catalyst loading: 400 mg;
reaction temperature: 350 ℃;
reaction pressure: 0.1 Mpa;
synthesis gas space velocity: 15000 mL/g.h.
The composition of raw material gas and catalytic reaction conditions applicable to the catalyst of the invention can also be as follows: the volume airspeed of the synthesis gas is 3000-30000 mL/g.h, the pressure is from normal pressure to 3.0Mpa, the temperature is 200-600 ℃, and H in the synthesis gas2The ratio of/CO is 2-4.
CO conversion and CH were determined and calculated as follows4The selectivity, results are shown in table 1:
conversion rate of CO: xCO＝(1-amount of CO contained in product/amount of CO contained in feed gas) x 100%
CH4And (3) selectivity: sCH4(generated CH)4Amount/1-amount of CO contained in the product). times.100%
Comparative catalysts D1-D3, specified below:
comparative catalyst D1: 1.0g of SBA-15 is taken as a carrier, and 0.30g of nickel nitrate hexahydrate is dissolved in 7g of deionized water; soaking SBA-15 in the solution for 12h, after the soaking, drying in vacuum at 50 ℃ for 12h, then roasting in air at 500 ℃ for 5h, and naturally cooling to room temperature to obtain the Ni/SBA-15 catalyst, which is recorded as 5% Ni/SBA-15 (D1).
Comparative catalyst D2: with 1.0g of Al2O3Using the carrier, the same procedure as in comparative example catalyst D1 was repeated to obtain Ni/Al2O3Catalyst, 5% Ni/Al2O3(D2)。
Comparative catalyst D3: at 1.0g SiO2As a support, the remainder was made into Ni/SiO in the same manner as in comparative example catalyst D12Catalyst, 5% Ni/SiO2(D3)。
As shown in FIG. 5, FIG. 5 is a graph comparing the catalytic performances of the catalysts of examples 2-5 and comparative examples D1-D3 when applied to methane production from synthesis gas. As can be seen from FIG. 5, the perovskite-type composite oxide-based multi-metal methanation catalyst shows excellent catalytic performance in the CO methanation reaction, the CO conversion rate reaches more than 92% at the reaction temperature of 350 ℃, and CH (carbon-oxygen) is obtained4The selectivity reaches more than 90 percent. At the same time, the addition of the third metal results in both CO conversion and CH4The selectivity is improved, and the catalyst LaMo is0.3Ni0.7O3SBA-15 CO conversion up to 99.3%, CH4The selectivity reaches 98.4 percent. While in the comparative example 5% Ni/SBA-15(D1), 5% Ni/Al2O3(D2) And 5% Ni/SiO2(D3) The CO conversion of (C) was only 89.9%, 64.2% and 56.6%, CH4The selectivity is lower than 80%, which shows that the multi-metal methanation catalyst prepared based on the perovskite type composite oxide has high catalytic activity in the CO methanation reaction.
The invention is based on perovskite type composite oxide, through combining metal ion complex method and organic additive auxiliary impregnation method, and use stable, good heat conductivity of chemical property, mesoporous molecular sieve SBA-15 with large specific surface area as carriers to prepare the multi-metal methanation catalyst with active component fully contacting with the auxiliary metal and highly dispersing in the carrier pore canal, the obtained multi-metal methanation catalyst has the advantages of high catalytic activity, good methane selectivity, excellent heat resistance, longer catalyst life and the like, and has great industrialization prospect. Meanwhile, the preparation method also provides thinking and theoretical guidance for the design and preparation of other high-dispersion limited-area multi-metal catalysts.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1, multi-metal methanation catalyst, which is characterized in that the catalyst is based on perovskite type composite oxide and highly dispersed in the pore canal of mesoporous molecular sieve SBA-15, the perovskite type composite oxide is La1-xAxB1-yNiyO3X is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, A is at least of alkali metals, alkaline earth metals and rare earth metals, B is at least of transition metals, the loading capacity of La is 1-10 mol%, the loading capacity of A is 1-10 mol%, the loading capacity of B is 1-10 mol%, and the loading capacity of Ni is 1-10 mol%.
2. The multimetallic methanation catalyst of claim 1, wherein: the mesoporous molecular sieve SBA-15 has the pore size of 4.6-30 nm, the pore wall thickness of 3-9 nm and the pore volume of 0.8-1 cm3A/g, preferably 0.85cm3/g。
3. The multimetallic methanation catalyst according to claim 1, characterized in that the alkali metal is at least of Rb and Cs, the alkaline earth metal is at least of Mg, Ca, Sr and Ba, and the rare earth metal is at least of Ce and Sm.
4. The multimetallic methanation catalyst of claim 1, wherein the transition metal is at least of Fe, Co, Ru, Rh, Cu, Mo.
5, method for preparing a multimetallic methanation catalyst as described in any of claims 1 to 4, , characterized by comprising the steps of:
, dissolving a lanthanum-containing compound, a metal A precursor, a metal B precursor and a nickel-containing compound in deionized water, stirring and dissolving, then adding a complexing agent and a solvent, wherein the ratio of the complexing agent to the total molar weight of the lanthanum-containing compound, the metal A precursor, the metal B precursor and the nickel-containing compound is (1-1.5): 1, and stirring to uniformly mix;
and secondly, soaking the mesoporous molecular sieve SBA-15 in the prepared mixed solution at room temperature for 2-12 hours, drying in vacuum at 40-60 ℃ for 6-8 hours after soaking, presintering at 300-500 ℃ for 2-3 hours, calcining at 600-800 ℃ for 4-6 hours, grinding into fine powder, and filtering by using a 100-mesh sample separation sieve to obtain the multi-metal methanation catalyst.
6. The method for preparing a multimetallic methanation catalyst of claim 5, characterized in that: the lanthanum-containing compound is lanthanum nitrate;
the precursor of the metal A is a compound containing metals, preferably Rb, Cs, Mg, Ca, Sr, Ba, Ce and Sm, and preferably magnesium nitrate, calcium nitrate and cerous nitrate hexahydrate.
7. The preparation method of the multi-metal methanation catalyst according to claim 5, characterized in that the metal B precursor is a compound containing metals, such as Fe, Co, Ru, Rh, Cu, Mo, preferably iron nitrate, cobalt nitrate, ammonium molybdate;
the nickel-containing compound is kinds of nickel nitrate and nickel acetate.
8. The preparation method of the polymetallic methanation catalyst according to claim 5, characterized in that the complexing agent is of citric acid, sodium acetate and glycine;
the solvent is ethylene glycol.
Use of the multimetallic methanation catalyst of any one of claims 1 to 4 to for the production of methane from synthesis gas.
10. Use of a multimetallic methanation catalyst according to claim 9 for the production of methane from synthesis gas, characterized in that: the conditions for preparing methane from the synthesis gas are as follows: the volume space velocity of the synthesis gas is 3000-30000 mL/g.h, the pressure is from normal pressure to 3.0Mpa, the temperature is 250-600 ℃, and H in the synthesis gas2The ratio of/CO is 2-4.
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